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Preparation method for 9-fluorenone and T type oligomeric phenylene skeleton compounds

A compound, polyphenylene technology, applied in the field of preparation of 9-fluorenones and their T-type oligophenylene skeleton compounds, can solve problems such as harsh reaction conditions, and achieve the effect of mild conditions and high-efficiency preparation

Active Publication Date: 2015-08-19
NANJING UNIV OF POSTS & TELECOMM
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, in most of the above cases, the synthesis of 9-fluorenones requires pre-functionalized reaction substrates, namely biaryl derivatives or diaryl ketones, or the reaction conditions are relatively harsh.

Method used

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  • Preparation method for 9-fluorenone and T type oligomeric phenylene skeleton compounds
  • Preparation method for 9-fluorenone and T type oligomeric phenylene skeleton compounds
  • Preparation method for 9-fluorenone and T type oligomeric phenylene skeleton compounds

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0067] Example 1: Under nitrogen protection, add phenylboronic acid (0.6mmol, 73.2mg), cesium carbonate (1.5mmol, 489mg), palladium acetate (0.025mmol, 5.6mg) in a Schlenk reaction tube, and place in glove box Add tricyclohexylphosphine (0.05mmol, 14mg), take it out and replace it with CO gas atmosphere, add o-bromoiodobenzene (0.5mmol, 64.2uL) and pivalic acid (0.5mmol, 51mg) to the system successively, and then After adding 3 ml of toluene and stirring for 5 minutes, the reaction was placed in an oil bath at 100° C. for 12 hours. After the reaction was over, 3 milliliters of saturated ammonium chloride solution was added to the system to quench the reaction, and 15 milliliters of ethyl acetate was added for extraction three times. The organic phases were combined, dried over anhydrous sodium sulfate, and separated by column chromatography to obtain the product. The yield was 90% (see Table 1 for details).

Embodiment 2-13

[0068] Embodiment 2-13: Except for using different aryl boronic acids, other reaction conditions are the same, specifically as follows:

[0069] Under nitrogen protection, add arylboronic acid (0.6mmol), cesium carbonate (1.5mmol, 489mg), palladium acetate (0.025mmol, 5.6mg) in a Schlenk reaction tube, and place in a glove box, add tricyclohexylphosphine (0.05mmol, 14mg), after taking out, replace it with CO gas atmosphere, add o-bromoiodobenzene (0.5mmol, 64.2uL) successively in the system, pivalic acid (0.5mmol, 51mg), then add 3 milliliters of toluene, stir 5 Minutes later, the reaction was placed in an oil bath at 100°C for 12 hours. After the reaction was over, add 3 milliliters of saturated ammonium chloride solution to the system to quench the reaction, add 15 milliliters of ethyl acetate for extraction three times, combine the organic phases, dry with anhydrous sodium sulfate, and separate the product by column chromatography (see Table 1).

Embodiment 14

[0070] Example 14: Under nitrogen protection, 9,9 dioctylfluorene-1,3,2-propanol borate (0.6mmol, 262mg), cesium carbonate (1.5mmol, 489mg) were added to a Schlenk reaction tube, Palladium acetate (0.025mmol, 5.6mg), and placed in the glove box, added tricyclohexylphosphine (0.05mmol, 14mg), replaced with CO gas atmosphere after taking it out, and added o-bromoiodobenzene (0.5mmol, 64.2uL), pivalic acid (0.5mmol, 51mg), then 3ml of toluene was added, and after stirring for 5 minutes, the reaction was placed in an oil bath at 100°C for 12 hours. After the reaction was over, 3 milliliters of saturated ammonium chloride solution was added to the system to quench the reaction, and 15 milliliters of ethyl acetate was added for extraction three times. The organic phases were combined, dried over anhydrous sodium sulfate, and separated by column chromatography to obtain the product. The rate was 45% (see Table 1 for details).

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Abstract

The invention relates to a preparation method for 9-fluorenone and T type oligomeric phenylene skeleton compounds. The method includes: under the condition of 90-100DEG C, in a toluene solution, taking palladium acetate and tricyclohexylphosphine as the catalytic system, and adopting cesium carbonate as alkali, reacting o-dihalogenated aromatic hydrocarbon with arylboronic acid or aryl boric acid ester under CO atmosphere for 12h, thus obtaining a series of 9-fluorenone and T type oligomeric phenylene skeleton compounds. The method provided by the invention adopts simple, economical and easily available raw materials as the substrate, under the CO balloon pressure, palladium catalyzed carbonylation three-component cascade reaction is carried out to realize synthesis of 9-fluorenone compounds. Through bifunctionalization, Pi conjugated system expanded T type oligomeric phenylene skeleton compounds that are difficult to realize by previous methods can be constructed by one step, and the compounds have very great application prospects in pharmaceutical synthetic intermediates and organic photoelectric material science.

Description

technical field [0001] The invention belongs to the field of organic synthesis, and in particular relates to a preparation method of 9-fluorenones and T-type oligophenylene skeleton compounds thereof. Background technique [0002] 9-fluorenone compounds widely exist in nature and natural products, and are key intermediates in the synthesis of many biomedical molecules. By functionalizing carbonyl and diaryl rings, a series of fluorenyl-based material molecules with variable structures can be obtained. In the past forty years, with the development of organic semiconductor materials, fluorenyl-based material molecules have become popular due to their special photoelectric properties. The most important structural framework in the field of organic photoelectric materials is widely used in organic or polymer light-emitting diodes (OLEDs), organic solar cells (OPVs), organic field-effect transistors (OFETs) and other fields. [0003] As far as the synthesis of fluorenone-based m...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07B41/06C07C45/49C07C49/675C07C49/755C07C49/697C07C49/757C07C49/665C07C67/343C07C69/76C07C253/30C07C255/56C07D333/74C07D209/94
Inventor 宋娟魏福亮孙威李亚丽解令海
Owner NANJING UNIV OF POSTS & TELECOMM
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